Process for production of aluminum chloride and other products from carbonaceous shales and like material



Aug. 26 lm PROCESS FOR PRODUCTION 0F ALUMINUM CHLORIDE AND OTHER PRODUCTS FROI CARBONACEOUS SHALES AND LIKE MATERIAL Original Filed Oct. 13. 1919 E. R. WOLCOTT 3 Smets-Shuiv 1 BV web 10. A/myu A TTOHNE Y Aug. 426, B924. 1,506,104

E. R. WOLCOTT PROCESS FOR PRODUCTION OF ALUMINUM CHLORIDE AND OTHER PRODUCTS FROM CARBONACEOUS SHALES AND LIKE MATERIAL Original Filed Oct. 13 1919 3 SheetBLSheet 2 carbans Augn 26 Q 192% 1,506,104

E. R. WOLCOTT PROCESS FOR PRODUCTION OF ALUMINUM CHLORIDE AND OTHER PRODUCTS FROM CARBONACEOUS SHALES AND LIKE MATERIAL Original Flled Oct. 13, 1919 3 Sheets-Shoot 3 Patented ug. 26, 1924.

UNITE STATES isolati EDSON.'` R. WOLCOTT, OF LOS ANGELES, CALIFORNIA, ASSIGNOR, BY MIESNE ASSIGN- MENTS, TO THE TEXAS COMPANY, OF NEW YORK, N. Y., A CORPORATION OF TEXAS.

PROCESS FOB PRODUCTION OF LUMINUH CHLOBIDE AND OTHER, YRODUCTS FROM CARBONACEOUS SHALES AND LIKE MATERIAL.

Application led October 13, 1919, Serial No. 330,381. Renewed February 18, 1922. Serial No. 537,645.

To all whom t may concern:

Be it known that l, EDsoN R. WoLoo'rr, a citizen of the United States, residing a'. Los Angeles, in the county of Los Angeles and State-of California, have invented a new and useful Process for Production of Aluminum Chloride and Other Products from Carbonaeeous Shales and like Material, of which the following is a specification.

This invention relates to the production yof aluminum chloride and other products from materials containing aluminum silicate, and the main object of the invention is to provide for economical production of aluminum chloride, or sodium aluminum chloride, by the' utilization of carbonaceous argillaceous minerals, such as the so-called oil shales, or shales containing carbonaceous matter, as material for producing the aluminum com und and also for furnishing vthe fuel required for the production of such compound. In this connection another object of the invention is to rovide for the production of by-products rom the carbonaceous constituent of the shale, and also in some cases for the utilization of the carbonaceous constituent of the lshale for other purposes, for example, for the production of power by combustion of certain of such products.`

The accompanying drawings illustrate more or less dlagrammatically t e apparatus suitable for carrying out the invention, and referring thereto:

Fig. 1 is a vertical section of the furnace or retort in,A which the shale or other aluminum-bearing material is treated, showing diagrammaticall the connections 'therefor for treatment o the several products from such retort. .Y

Fig. 2 is a view similar t0 Fig. 1 showing the connections required for production of special by-products from the carbonaceous or hydrocarbon constituent of the material being treated.

Fig. 3 is a view similar to Fig. 1 showing the connections required for carrying out the process when a halogen salt, such asv sodium chloride, is used as the chloridizing agent For treatment of the aluminum-bearing material.

My invention is particularly applicable to the production of aluminum chloride from carbonaceous shales, such as bituminous or oi-l shales, or other argillaceous materials containing hydrocarbons or carbonaceous substances, and in this connection the invention will be described with particular reference to the treatment of oil Shales socalled, that is to say, shales which upon destructive distillation yield more or less hydrocarbon or petroleum product. lit will be understood, however, that the invention is applicable to other clay substances, such as argillaceous fuels including slaty coal, or shale containing coal, impure or low grades of lignite or coals, and generally to any material containing alumina or aluminum silicate and carbon or carbonaceous material. rl`he invention contemplates the treatment of a carbonaceous argillaceous mineral, comprising alumina or aluminum silicate and carbonaceous material, of such nature as to be capable of yielding on heating or distillation vaporous hydrocarbon products and a residue containing carbon and aluminous material adapted for reacting with added chlorin to form aluminum chloride.

The apparatus shown on the drawing in Fig. 1 comprises a retort 1 formed, for example, as a vertical cylinder of suitable materialhaving an inlet 2 at its upper end through which the material to be treated is fed into the retort and an outlet 3 at its lower end throu h which waste material may be'drawn. uitable means, such as a hopper 4, provided with feed means, not shown, may be rovided at the upper end of retort 1 for fee ing into the retort 1 the oil shale, or other material, after same has been crushed or reduced to a suitable size by a crusher indicated at 5.

The retort 1 is surrounded by a casing or enclosing means 7 forming a combustion and heating chamber 8 around said retort, said 'chamber being heated by suitable burner means indicated at 9 and having an outlet 10 at its upper end for the products of combustion. W0 pipe lines or conduits 11 and 12 lead from the upper part of retort 1. said pipe lines or conduits being provided with 'valves or dampcrs 13 and 14.- whereby they maybe opened alternately, as hereinafter set forth.

The pipe line 11 is for conducting away the hydrocarbons, or other carbonaceous gases and vapors produced by the destruc-4 tive distillation of the oil shale and may be connected to a condenser 15 and means 16 for receiving the condensed products. A connection 17 having a pump 18 may be provided for drawing uncondensed gases and vapors from the receiving means 16 or from the pipe line 11 and forcing same into a suitable means, such as a gasometer or gas reservoir 19 for storing such gases or vapor products of the distillation. A pipe connection 20 maylead from this storage reservoir to the burner 9 so as to heat the oil shale by combustion of the gas derived from destructive distillation thereof.

Pipeline 12 leads through fa condenser 22 to suitable filter or precipitator means 23 for removing from the gases passing thereto the material condensed in the condenser 22.

i outlet 28 for the collected material and with another outlet 29 leading to a purifying apparatus shown as a revolving drum 30 1n the furnace chamber 31 heated by burner means 32, said revolving drum opening into a settling chamber 33 from which a conduit 34 leads to a filter or precipitator 35. From said iilter or precipitator a connection- 36 conducts the filtered or precipitated maferial to' a storage tank 37. From said tank the material may pass through one or more of several different operations, as hereinafter described, according to the product which it is desired to produce.

The process may be carried out in the above described apparatus in the following manner: The oil shale or similar material is passed through the Crusher 5 so as tobe reduced to a suitable state of division, preferably in the form of lumps or fragments suliciently small to present a large surface to the heating action and sufficiently large to enable free passage of the chloridizing gases through and free delive l of the volatilized vapors from the material. For this purpose the material may be crushed to, say, one-half inch mesh or thereabout. The material isisupplied through the inlet tube of,

inedite 1, resulting in destructive distillation thereof and the volatilization of carbonaceous vapors, mainly hydrocarbons, which pass off through pipe l1 and are cooled in condenser 15 so as t0 liquefy the more condensible constituents thereof, forming oils which collect in receptacle 16, the residual gas and vapors being drawn oil to the storage tank 19. When suiiicient combustible gas has been accumulated in this manner in the stora e tank 19, a portion thereof may be drawn t rough outlet pipe 20 to the burner 9 for continuing the heating of the retort 1. Any excess of gas not required for this purpose may be delivered to any other desired consuming device by branch pipe, 42. For example, it may pass to a power plant, indicated at 38,- using hydrocarbon for the generation of power to operate a dynamoelectric generator 39, which suppliescuri'ent through leads 49 to an electric furnace 50 used in connection with the process. The oil accumulating in the receptacle 16 may, if desired, be passed ofi' through pipe' 43 and treated in anysuitable manner (in refining or distilling apparatus indicated at 41), if desired, for producing one or more commercial products, or such oil, or the residuum after such treatment, may be passed to a burner 44 for assisting in the heating operation in the combustion chamber 8. Any valuable hydrocarbon by-products produced in the apparatus 41 may be led ofi' by pipe 39 and utilized in any suitable manner. Or, if desired, part or all of the oil or liquid hydrocarbons produced from the condenser 15 may be drawn ofi' through pipe 43 for use or sale as such.

When lthe destructive distillation of the carbonaceous content of the oil shale has been completed by the above described operation (which will, in general, be determined by the cessation of flow of'the h drocarbon gases and vapors through tlie pipe line 11), the said pipe line is closed by damper 13 and damper 14 for t-he pipeline 12 is then opened and the recess then passes Ato `the second stage o distillation jwhich consists in a chloridizing volatilization of the aluminum content of the clay. In this connection, it is necessary to use a chloridiz'ing agent, or volatilizing agent. and for this purpose I prefer r'to use gaseous. chlorine introduced through the iiilet 46, 'which opens intov the outlet 3 of the retort isc atomes l. immediately following the completion of the first or destructive distillation and while the residual material in the retort is still hot, the chlorine is turned on or admitted through the pipe 46 from any suitable source, indicated as a storage tank/48, and the heating is continued, the retort l being maintained at a suitable temperature by continuedadmission of fuel to one or 'more of the burner means 9, or 44, aforesaid. The aluminum silicate present in the I clay or shale residue is in intimate contact with carbon distributed throughout the mass of said clay or shale, such carbon being the residuum from the destructive distillation of the carbonaeeous content of the clay or shale. The fragments of clay or shale are also in contact with chlorine assing upwardly through .the retort l. nder the action of the heat maintained in said retort and in the presence of the said carbon and chlorine, the action takes place in such manner that aluminum chloride is produced, and being volatile at the temperature 0f operation passes off through the pipe line l2. Passing through the condenser 22 the aluminum chloride is condensed from the fume, which is collected in the filter or precipitator 23, passing therefrom to the receptacle 26. The aluminum chloride so collected will generally be in the form of a fine powder containing more or less impurities, especially ferrie chloride, derived from impurities in the original clay or shale. In some cases, however, the product may be sufficiently pure for use and sale as commercial aluminum chloride and may be withdrawn for that purpose through outlet 28.

In case further purification is desired the aluminum chloride may be passed through conduit 29 to the re-volatilizing drum 30, wherein it is subjected to sufficient heat to volatilize the aluminum chloride, while leaving other materials, for example, ferrie chloride, in un-volatilized condition. Such other materials pass out as waste, as indicated at the lower end of the drum 30. The vapor of aluminum chloride issuing from the drum 30 passes through chamber 33 wherein any dust passing over with same is settled out and then passes toy the filter or precipitator 35, which collects .the fume pf the condensed aluminum chloride and discharges the same into the storage tank 37. Aluminum chloride so produced may be used or sold for use for ordinary'commercial purposes, for example, as an agent in petroleum refining. It may, however, if desired, be used for production of metallic aluminum, andin that case aluminum chloride from the receptacle 37 may be electrolyzed in the electric furnace 50 to produce metallic aluminum and chlorine (the latter being delivered to tank 48 aforesaid), or, if

lduce anhydrous alumina and t0 drive oii the hydrochloric acid gas, which may be sold or utilized as such, or may pass through a catalytic chamber 55 wherein it is brought in contact with a suitable catalytic agent, such as heated cupric chloride,

in the presence of oxygen or air introduced at 59 to produce water and chlorine. The water is removed in the condenser or dehydrator 57 and the free chlorine passed to tank 48. Any chlorine required in the process, in addition to that recovered from the above described operations, may be supplied from any suitable source.

ln the above described embodiment of my invention, the carbonaceous or hydrocarbon products of the first distillation are utilized both for heat production and for power generation in connection with the process, and any surplus of power or of fuel may be utilized in any suitable manner. It will be understood that in order to provide for continuous operation, duplicate retorts 1 may be provided and operated alternately so that one retort may be always in condition to deliver fuel for the stated purposes. lf desired, however, this can be provided for by making the storage means 16 and 19 of suficient capacity. ln special cases it may be vdesirable to use a` major part of the fuel products of the process in the production of power, and in case the power plant is adapted to use the crude product, the latter may be led directly to said plant from the pipe 11.

ln many cases the amount of carbonaceous material contained in the clay material under treatment is not sulicient to provide the fuel required for distillation purposes or the fuel required for power generation in connection with the process, or for both of such purposes, and, in such cases, it is desirable to subject an additional quantity of the carbonaceous or oil shale, etc., to suit'- able treatment, for.the production of fuel therefrom; for this purpose such additional quantity of the oil shale may (either with or without preliminary heating in any suitable retort to first drive olf the hydrocarbons, which may be utilized as above described) be subjected while at high temperature toy the action of steam or of air, or both, to make producer gas, the resultant gases being introduced into the combustion chamber of the retort l, or into the combustion chamber of the power generating plant or apparatus 38, for the generation of electrical current for use in connection with the processand, in such cases, the amount of additional oil shale, or carbonaceous shale, or low grade coal, used in this manner is not necessarily limited to what is required for carrying out thecdistilling operations aforesaid and for producing the power for electrolysis in connection with the above described process, butmay be made as auxiliary to or in connection with a power plant for general power generating purposes. rllhis treatment of additional oil shale, etco, for the product-ion of additional fuel may be carried out in an auxiliary retort or producer Iindicated at 58, discharging by the' pipe 59 to pipe 20 leading to the combustion chamber 8 and by pipe 59 tothe power plant 38.

In some cases it may be desirable to utilize the hydrocarbon products of the destructive distillation of the oil shale, etc., in the production of valuable by-products. ln this connection, the chlorine supply provided in connection with the second stage of distillation may be advantageously utilized in the formation ofsuch by-products, the hydrocarbons being'subjected to the action of such chlorine to produce substitution or addition products, as may be desired. A ilow sheet for such an embodiment of my invention is shown in Fig. 2 wherein the retort and the two pipe line connections therefrom are similar to those shown in Fig. 1, but there is provided in addition a catalyzing chamber 60 adapted to receive hydrocarbon gas or vapor from a suitable part ot the connections to pipe line 11 (for example, from gas holder 19), and to also receive chlorine from a connection 64, said catalyzing chamber being provided with means such as a `jacket 7 6 provided with piping 7 7 for passing a heatin medium therethrough for maintaining t e proper conditions of temperature to cause -reaction of the chlorine with such hydrocarbon to produce the desired chlorinated hydrocarbon product. As an illustration, the process may be used to produce carbon tetrachlorid, ethylene dichlorid, or other substitution or addition products, which constitute commercial products vand may be sold as such, or may be used for production of other hydrocarbon derivatives. These products may be discharged through pipe 61 to a separator 73 from which the residual gases, including residual hydrocarbon gases pass by pipe Td to combustion chamber 8.

The chlorine required for the process may conveniently be produced by electrolysis of sodium chloride in an electrolyzer 63, the chlorine passing to the drier and then by pipe 64: to the catalyzing chamber 60, and by pipe 62 to the chlorine inlet 46- of the retort l. The sodium hydrate from the electrolyzer 63 may pass through the stages of evaponation and fusion as indicated to form a commercial product.

lntreating the product of the second dis incarna tillation (consisting essentially of aluminum chloride) for the production of aluminunnl may first convert the aluminum chloride to alumina, as above described and as indicated at 52, and then electrolyze such alumina in an electric furnace, as indicated at 66 in Fig. 2. The hydrochloric acid produced in tank or chamber 52 may be decomposed in electrolyzer 67 to produce chlorine, which. nis returned by pipe 68 to drier 65 and hydrogen, which'may be used for hydrogenation, in an apparatus indicated at 69, of one or more of the hydrocarbon derivatives roduced from the products of the first dist1llation. Similar disposition may be made of the hydrogen from the electrolyzer 63. Or the hydrogen can be compressed and'sold as a commercial article.

ln some cases, I may use sodium chloride, or an equivalent salt, instead of gaseous chlorine as a chloridizing agent in the second distillation, the sodium chloride, or other salt, being introduced at 70, as shown in- Fig. 3, into the retort 1, and the volatilized product in that case being mainly a double chloride of sodium and aluminum. This double salt may be purified, if necessary, in apparatus 30, and then electrolyzed in an electric furnace 71, producing metallic aluminum and gaseous chlorine. Such chlorine is advantageously returned to the retort 1, as it is desirable to furnish a certain amount of free chlorine, together with the sodium chloride, to ensure e'ective volatilization of the sodium-aluminumchloride. The operation may be otherwise carried out in the same mannerv as described in connection with Fig. l or Fig. 2.

In any of the above described embodiments of my invention, the waste or residual material from the final distillation and consisting mainly of siliceous gangue, is withdrawn at the end of the operation through outlet 3 and the retort 1 then charged with fresh material for repetition of the operation.

ln general the shale to be treated contains considerable water and, in case it is desired to eliminate this before the tiret distilling operation, the water vapor may be carried oit through a pipe 21a, see Figs. 1, 2 and 3, so as not to mix with the hydrocarbon products. in case the clay used contains an appreciable amount of iron, this may be eliminated by passing hydrochloric acid through gas inlet i6 into the retort 1, after the water has been eliminated and preferably after the hydrocarbons have been distilled oit. By passing hydrochloric acid in contact with dry clay at a suitable temperature, sa about 900 C., li am enabled to drive ofi all the iron as a volatile compound, leaving the aluminum compound mainly.7 una'ected, so that in the ensuing or final distillation aluminum chloride is produced in accenni pure condition. 'llhe same operation may be effected by passing hydrochloric acid trom stage 52 (1n Fig. 2) to retort l.

As an alternate method of `freeing the alumina produced by my process from iron and other impurities, l( may treat the alumina (produced at stage 52 in lFigs. l and 2) with caustic soda solution to form alu'- minate, and then precipitate the alumina by reaction with alumina or with CQ, in Well known manner, or other methods ci purification may be used.

l/Vhat l claim is: i

1. The process of making aluminum chloride comprising reacting with a chlori-A dizing agent u on a distillation residue derived from car onaceous shale, said residue comprising aluminum silicate having carbon intimately associated therewith.

2. The recess which consists in subjecting a car onaceous argillaceous mineral to heat to eect destructive distillation in such manner as to volatilize hydrocarbon compounds, then, while maintaining the material in heated condition, introducing a chloridizing agent into Contact with said material, to heat to volatilize and driveoti' aluminum chloride, and collecting said aluminum chloride.

3. The process which' consists in subjecting carbonaceous shale to heat to eidect destructive distillation to volatilize and drive off hydrocarbon compounds and to leave residual carbon in the material being treated, then While continuing the heating operation introducing chlorine into contact `With the residual material and subjecting the material to further distillation to volatilize aluminum chloride, and collecting said aluminum chloride.

4. The process Which consists in subjecting a carbonaceous argillaceous mineral to sulcient heat to drive of hydrocarbons leaving residual carbon in the material, then introducing a chloridizing agent to the residual material and subjecting the same to further heat to volatilize a compound of aluminum and chlorine, condensin said compound of aluminum and chlorine and recovering the same separately from the hydrocarbon compound aforesaid.

5. The process which consists in subjecting material containing a carbonaeeous argillaceous mineral to 'a drying operation to remove moisture therefrom, then heating operation sutiicient to volatilize hydrocarbon compounds from thel carbonaceous material, then introducinghydrochloric acid and' continuing the heating at suiciently high tempera-ture to volatilize as 'ferrie chloride any iron present in the residual material, and then passing chlorine into the residual material containing aluminum silicate and residual carhon and subjecting the material to to produce' and volatiiiae aluminum resi chloride, and collecting such aluminum chloride. y

6. The process which comprises subjecting to heat a carbonaceous argillaceous mineral to eect destructive distillation in such manner as to vo atilize and drive oil'a hydrocarbon compounds, leaving a residual material .containing aluminum silicate and re sidual carbon in intimate association, subjecting the residual material to heat in the presence of a chloridizing agent to produce and volatilize aluminum chloride, condensing and collecting the aluminum chlo- Iintimate association, eontactingthe residual material with a chloridizing agent While continuing the heating operation to produce anhydrous aluminum chloride in a volatile state.

8. The process of making aluminum chloride comprising reacting With chlorin upon a residue derived from heating a carbonaceous argillaceous mineral, said residue comprising aluminousmaterial and carbon.

9. The process of making aluminum chloe ride comprising contacting a chloridizing agent With a heated residue derived from a carbonaceous argillaceous mineral.

i0. The process of making aluminum chloride that comprises heating a carbonaoeous argillaoeous mineral containing aluminous material and carbon in intimate asso-1 ciation and contacting said mineral With a chloridizing agent.

1l. 'llhe process of making aluminum vchloride that comprises heating material comprising a carbonaceous argillaceous mineral containing aluminum silicate and carbon in intimate association and introducing a chloridizing agent into contact with said mineral.

l2. "ihe process of making aluminum chloride that comprises reacting with a chloridizing agent upon a residue derived from heating an argillaceous fuel.

i3. rihe process that comprises subjecting a careonaceous argillaceous mineral to heat to drive oli hydrocarbon products, con-.tacting 1 e residual material with a chloridizing agenJ nils applying heat produce alumif lid@ llO

num chlorideJ vapors, condensing and collecting the aluminum chloride thus produced, treating said aluminum chloride electrolytically to produce aluminum and chlorin and assing said chlorin Eind aforesaid hydrocarbon products in contact with heated catalytic material to form chlorinated hydrocarbons.

14. The process that comprises subjecting a carbonaceous argillaceous mineral to heat to drive oilq hydrocarbon products, contacting the residual material with a chloridizing agent while applying heat to produce aluminum chloride vapors, condensing and collecting the -aluminum chloride thus produced, hydrolyzing said aluminum chloride to form hydrated alumina and HC1, treating said products electrolytically to produce aluminum from said alumina and hydrogen. and chlorin from the HC1 and contacting said hydrogen with aforesaid hydrocarbon products under conditions to form hydrogenated products.

15. The process that comprises heating a carbonaceous argillaceous mineral to drive ofi' hydrocarbon vapors and obtain a residue comprising an aluminous material and carbon, treatin a solution of sodium chlorid electrolytica ly'and introducing the chlorin derivative ofvthe electrolysis into Contact with said residue While applying heat to same to generate aluminum chloride vapors, collecting said aluminum chloride and passing the hydrogen derivative of aforesaid electrolysis into contact with aforesaid hydrocarbons under conditions to form hydrogenated products.

In testimony whereof AI have hereunto subscribed my name this 6th day of 0ctober 1919.

EDSON R. WOLCUTT. 

